Detergent compositions



3,000,831 DETERGENT COMPOSITIONS Melvin E. Tuvell, Los Angeles, Calif., assiguor to Monsanto Chemical Company, St. Louis, 'Mo., a corporation of Delaware No Drawing. Filed July 22, 1957, Ser. No. 673,161 13 Claims. (Cl. 252-438) This invention relates to the preparation of improved heavy-duty detergent compositions which are particularly suitable for use in automatic washing machines.

Various heavy-duty detergent compositions have been proposed and introduced into commercial practice. Many of these detergent'compositions are built formulations essentially containing a minor amount of a nonionic or anionic surface-active agent; various alkaline metal phosphates such as sodium tripolyphosphate, tetrasodium pyrophosphate, and mixtures thereof; other alkaline materials such as sodium carbonate and sodium bicarbonate; and various soluble alkaline metal silicates as corrosion inhibitors therein. The formulations may also contain other salts such as sodium sulfate, sodium borate, etc., and relatively small amounts of other additives as for example an antisoil redeposition agent such as carboxymethyl cellulose, and dyes, perfumes, etc., as desired.

These prior art detergent formulations have given excellent service particularly as controlled suds formulations for use with automatic washers. However it'has subsequently been found that the aforesaid formulations may be found to contain varying amounts of a fine, insoluble, sand-like material which clings to the garments washed with said detergent and presents 'an objectionable appearance. This insoluble material has been identified as silicon dioxide and has been found present in an amount of up to about 6 percent by weight of commercial, detergent compositions and under extreme conditions the insoluble content of the formulation can vary up to about 8 percent. The formation of the insoluble silicon dioxide is caused by the degradation of the soluble silicates employed in the detergent compositions and may become a serious problem where the detergent composition has been subjected to relatively high temperatures during transportation and storage and/or has been held for a long period of time prior to use. For example three widely distributed commercial built detergent compositions when subjected to an elevated temperature for a period of up to 48 hours were found to contain the fol lowing percent of 'insolubles, on a dry basis: I, 3.12; H, 5.72; and III, 6.29. Relatively long standing of the detergent composition in free contact with theair after the container has been opened also has been found to accelerate the formation of the insoluble silicon dioxide.

It is the principal object of this invention to provide improved heavy-duty detergent compositions which are stable for relatively long storage periods and are stable at relatively high temperatures as may be encountered in truck bodies, railroad cars, storage areas, and the like. Another object of this invention is to provide controlled -able for use in automatic washing machines. Still nited States Patent 3,000,831 Patented Sept. 19, 1961 tions containing soluble silicofluorides and preferably soluble alkaline metal and alkaline earth metal silicofluorides, wherein ammoniumis treated as an alkaline metal, in an amount of from about 2 to about 9 weight 1 percent and preferably from about 3 to about 5 weight percent, based on the detergent composition, are characterized by a material improvement in their ability to withstand relatively high temperature and long storage time without the formation of excessive insoluble ma terial. Illustrative built detergent compositions, wherein all parts are parts by. weight, are generally defined by the formulation essentially containing:

The improved detergent compositions can also include minor amounts of other materials as desired such as antisoil redepositionagents, optical brighteners, dyes, perfumes, foam stabilizers, and the like.

The nonionic surface active agent can be a condensation product of the lower alkylene oxides containing up to 4 carbon atoms, for example, ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, with a compound, or compounds, having one or more active hydrogen atoms, as for example, aliphatic mercaptans, alkyl phenols, fatty acids, alcohols, amines, and the like, which compounds preferably have a molecular weight of less than about 400. The mole ratio of the alkylene oxide to the active-hydrogen-containing compound is from about 3 to' about 20 and preferably from about 9 to about 15. illustrative nonionic surface active agents are: tertiary dodecyl mercaptan with 10 moles of ethylene oxide, tertiary nonylphenol with 15 moles of ethylene oxide, dodecylphenol with 10 moles of ethylene oxide,

tetradecylphenol with 12 moles of ethylene oxide, tall oil fatty acids with 11 moles of ethylene oxide, tall oil fatty acids with 15 moles of ethylene oxide, n-tetradeoanol with 10 moles of ethylene oxide, S-ethylnonanol-Z with 15 moles of ethylene oxide, cocoanut oil alcohols with 10 moles of ethylene oxide, 2-butyloctanol-l with 10 moles-of ethylene oxide, dodecanol with 2 moles of propylene oxide plus 6 moles of ethylene oxide, octadecanol with 18 moles of ethylene oxide, hexadecanol with 4 moles of propylene oxide plus 16 moles of ethylene oxide, hexadecylamine with 4 moles of propylene oxide plus 12 moles of ethylene oxide, and the like.

The anionic surface active agents can be selected from the group comprising the sodium alkyl sulfates, the sodium alkyl sulfonates, the sodium alkylaryl sulfonates, the sodium salts of esters of polyhydric alcohol-sulfonates, the sodium salts of sulfated or sulfonated alkyl amides, the sodium salts of sulfated or sulfonated esters, and the like, such as sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium glyceryl monolaurate sulfate, sodium 1-(N,N oleyl methyl)arninoethane sulfonate, sodium methyl laurate sulfonate, and the like.

The illustrative detergent compositions containing the selected silicofiuoride were found to have substantially equivalent detersive properties and possessed substantially similar favorable characteristics regarding the inhibition of corrosion to'soft metals as the similar prior art compositions containing the soluble alkaline metal silicates.

It has also been found that the combination of the silicofluorides with soluble silicates are eifective at concentrations appreciably lower than that required to af-' ford protection against the corrosion of soft metals when used alone. Accordingly, the soluble silicofluorides can be advantageously employed to replace the soluble alkali metal silicates of the prior art formulations in whole or in part.

The improved detergent compositions of this invention can be prepared by a dry-mix procedure, or can be formulated as a slurry and subsequently dried by spray drying, drum drying, or other suitable means, or can be employed as a heavy-duty liquid detergent composition.

The following examples are illustrative of the instant invention;

EXAMPLE 1 A detergent composition was formulated containing the following materials in parts by weight.

Formulation A Sodium carboxymethyl cellulose Perfume and dye Similar formulations wererprepared wherein various sodium silicate solutions were substituted for the sodium silicofluoride and water in the aforesaid detergent composition. The sodium silicate (38% solids) had a ratio of SiO :N=a O of 3.221 in Formula B, 2.9 in Formula C, and 2.6 in Formula D.

The aforesaid samples were confined in sealed containers and subjected to a temperature of C. for a period of 20 days. Then the percent of insoluble material in the detergent compositions was determined by the following procedure.

A two-gram sample of the detergent composition was weighed out and introduced into ml. of distilled water at about 140 F. while stirring at about 1200 r.p.m-. Agitation was continued for a 10-minute period and the contents of the vessel was then transferred to a weighed centrifuge tube and centrifuged for 10 minutes at about 16 G, then the supernatant liquor was poured off and the solid precipitate was washed with distilled water and again centrifuged for 10 minutes. Thereafter the water was poured off and the insoluble residue was dried to constant weight in an oven at C. the determination was run in duplicate for each sample evaluated.

The percent of insolubles, on a dry basis, was found to be as follows:

Formula Containing- Percent Insolubles Sodium silicofluorlde 1.1 Sodium silicate (SiOz:NagO=3. 7.7 Sodium silicate (SlOztNflzO 7.8 Sodium silicate (SiOztNMO 7.4

EXAMPLE 2 It wasv shown that prolonged exposure to the atmos phere Was a further major contributing factor to the formation of insoluble sand in the prior art detergent formulations. The absorption of carbon dioxide from the atmosphere followed by neutralization of the sodium silicate with the subsequent polymerization and precipitation of silicon dioxide was indicated to be the cause of sand formation by this means. According- 1y, to. evaluate the detergent compositions by an accelerated exposure test they were subjected to aeration by a relatively high-content carbon dioxide atmosphere.

A sample of the detergent composition was placed in a closed system and aerated by passing a mixture of nitrogen-carbondioxide therethrough for a period of four hours at about 23 C. The gas mixture contained 9.6 percent, by volume, carbon dioxide. Thereafter the percent of insoluble, on a dry basis, was determined as described in Example 1 and found to be as follows:

Formula Containing- Percent Insolubles Sodium silicofluoride 0.15 Sodium silicate (S1032N320=3.2) 4. 64 Sodium silicate (SiOmNaiO=2.9) 5. 31

The aforesaid examples clearly indicate the material superiority of the detergent compositions of this invention containing a soluble silicofluoride in place of'the silicate in Whole or in part.

Other illustrative detergent compositions which can be employed are for example as shown in the following table, wherein the components are expressed in parts by weight.

Formulations Component A B O D E F G H I J K L M N O P Q R 5 Sodium tripolyphosphaten 5O 5 40' 4O 22 25 30 30 25 45 25 35 45 Tetrasodium pyrophosph e 40 40 40 9 40 22 25 20 25 40 25 20 Potassium tripolyphosp l late u m, 9 20 e apo assium pyro osph e 7 w .20. p 15 Sodium carbonate 20 15 20. 10 5 16 25 2.4 v 21 10 10 10 See footnotes at end of table. 7

Oomponent Formulations H I J' K' L M N O P Q R 8 Sodium bicarbonate Sodium sesquicarbonate.. 18 18 Sodium silica Lithium silicofluoride .I

Dye

I Tall oil fatty acids11 moles ethylene oxide.

b Tertiary dodeeyl mereaptan-IO moles ethylene oxide.

* Tertiary tetradeeyl mereaptan-20 moles ethylene oxide.

* Tertiary octylphenolmoles ethylene oxide.

9 Tertiary nonylphenolmoles ethylene oxide.

1 Tertiary nonylphenol-IO moles ethylene oxide.

2 Tall oil fatty acids-l2 moles ethylene oxide.

11 Dodecylphenol10 moles ethylene oxide.

1 Hexadeoanol-4 moles propylene oxide plus 16 moles ethylene oxide. 3 Cocoanut oil alcohols-10 moles ethylene oxide.

k Tetradecanol-lO moles ethylene oxide.

I Hexadecylamine-4 moles propylene oxide+l2 moles ethylene oxide.

""""""" m 1 n o 15 k 7 HO o Mixture 10 parts nonylphenol-IO moles ethylene oxide and 5 parts sodium dudecylbenzene sultonate.

Polypropylene glycol ethylene oxide condensate. 0 Tall oil fatty acids-14 moles ethylene oxide.

v Sodium dodecylbenzene sulfonate.

q Sodium octadeeyl sulfate.

I claim:

1. A built detergent composition comprising (1) 20 to 60 parts of an alkali metal polyphosphate selected from the group consisting of sodium tripolyphosphate, tetrasodium pyrophosphate, potassium tripolyphosphate, tetrapotassium pyrophosphate, and mixtures thereof; (2)

10 to 25 parts of an alkaline material from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and mixtures thereof; (3) 2 to 9 parts of a water-soluble silicofluoride; and (4) 5 to 35 parts of a surface-active agent from the group consisting of anionic and nonionic surface-active agents, and mixtures thereof; wherein all parts are parts by weight; and which detergent composition is characterized by the stability thereof against the formation of a deleterious quantity of insoluble compounds when subjected to storage conditions and elevated temperatures, and by a substantial freedom from corrosion of soft metals.

2. The detergent composition of claim 1, wherein the water-soluble silicofiuoride is an alkaline metal silicofluoride.

3. The detergent composition of claim 1, wherein the water-soluble silicofluoride is an alkaline earth metal silicofluoride.

4. The detergent composition of claim 2, wherein the alkaline metal silicofluoride is sodium silicofluoride.

5. The detergent composition of claim 2, wherein the alkaline metal silicofluoride is potassium silicofluoride.

6. The detergent composition of claim 2, wherein the alkaline metal silicofluoride is lithium silicofluoride.

7. The detergent composition of claim 2, wherein the alkaline metal silicofiuoride is ammonium siliofluoride.

8. The detergent composition of claim 3, wherein the alkaline earth metal silicofluoride is magnesium silicofluoride.

9. The detergent composition comprising a mixture of wherein all parts are by weight.

10. The detergent composition comprising a mixture of the following essential ingredients:

Parts Sodium tripolyphosphate Sodium carbon 10 Sodium sulfate 25 45 Sodium silicofluoride 5 Condensation product of one mole tetradecanol with 10 moles ethylene oxide 7 Water 8 wherein all parts are by weight.

11. The detergent composition comprising a mixture of the following essential ingredients:

wherein all parts are by weight.

12. The detergent composition comprising a mixture of the following essential ingredients:

Parts Sodium tripolyphosphate 35 Sodium carbon 10 Sodium Sulfate 10 Sodium silicofluoride 5 Sodium dodecylbenzene sul-fonate 35 Water 5 wherein all parts are by weight.

13, The. detengqm 99111295191911 9 l 1 ii 3 mm? sf t ms. Cites! 9 {11 f u of the following essential ingredients:

V 7 UNITED STATES PgTEN'gg q i m *t p y o pha fi- -rw 4 1335,66 Bpair Nov. 21, 1933 Sudium garbnuate v l v Smiumsmfm 10 2213 4 71 steindqni Se,

wherein 11 parts are by wqight. 0

.9 2 14,1111 Reegl Sept. 26, 1939' 

1. A BUILT DETERGENT COMPOSITION COMPRISING (1) 20 TO 60 PARTS OF AN ALKALI METAL POLYPHOSHATE SELECTED FROM THE GROUP CONSISTING OF SODIUM TRIPOLYPHOSPHATE, TETRASODIUM PYROPHOSPHATE, POTASSIUM TRIPOLYPHOSPHATE, TETRAPOTASSIUM SYROPHOSPHATE, AND MIXTURES THEREOF, (2) 10 TO 25 PARTS OF AN ALKALINE MATERIAL FROM THE GROUP CONSISTING OF SODIUM CARBAONATE, SODIUM BICARBONATE, SODIUM SESIQAUICARBONATE, AND MIXTURES THEREOF, (3) 2 TO 9 PARTS OF A WATER-SOLUBLE SILICOFLUORIDE, AND (4) 5 TO 35 PARTS OF A SURFACE-ACTIVE AGENT FROM THE GROUP CONSISTING OF ANIONIC AND NONIONIC SURFACE-ACITVE AGENTS, AND MIXTURES THEREOF, WHEREIN ALL PARTS ARE PARTS BY WEIGHT AND WHICH DETERGENT COMPOSITION IS CHARACTERIZED BY THE STABILITY THEREOF AGAINST THE FORMATION OF A DELETERIOUS QUANTITY OF INSOLUBLE COMPOUNDS WHEN SUBJECTED TO STORAGE CONDITIONS AND ELEVATED TEMPERATURTES, AND BY A SUBSTANTIAL FREEDOM FROM CORROSION OF SOFT METALS. 